JP6651509B2 - 一成分系アミノ樹脂被覆材料 - Google Patents
一成分系アミノ樹脂被覆材料 Download PDFInfo
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- JP6651509B2 JP6651509B2 JP2017517020A JP2017517020A JP6651509B2 JP 6651509 B2 JP6651509 B2 JP 6651509B2 JP 2017517020 A JP2017517020 A JP 2017517020A JP 2017517020 A JP2017517020 A JP 2017517020A JP 6651509 B2 JP6651509 B2 JP 6651509B2
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- acid
- polyester polyol
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 48
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
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Description
(A) メラミン−ホルムアルデヒド樹脂、ベンゾグアナミン−ホルムアルデヒド樹脂及び尿素−ホルムアルデヒド樹脂からなる群から選択される、少なくとも1種のアミノ樹脂、
(B) ポリ(メタ)アクリラートポリオール(B1)、ポリエステルポリオール(B2)、ポリエーテルオール(B3)、アルキド樹脂(B4)及びポリカルボナートポリオール(B5)からなる群から選択される、少なくとも1種のヒドロキシル基含有ポリマー、
(C)
− ヘキサヒドロフタル酸無水物、
− トリメチロールプロパン、
− 任意に、少なくとも1種のジオール、
− 任意に、少なくとも1種の他のトリオール、
− 任意に、少なくとも1種の他の二酸若しくは三酸又はこれらの誘導体、
の重縮合により得られる、少なくとも1種の分枝したポリエステルポリオールであり、かつ、
ここで、ポリエステルポリオールの原料の酸基及びヒドロキシル基は、1:1〜1:1.95、好ましくは1:1.2〜1:1.8のモル混合比で使用され、かつ
ポリエステルポリオール中で、ヘキサヒドロフタル酸無水物を基準として化学量論的に、テトラアルコールは20%未満、好ましくは10%未満使用される、特に好ましくは使用されず、かつ
ポリエステルポリオールは、ジヒドロキシカルボン酸から形成されておらず、好ましくはポリヒドロキシカルボン酸からも形成されておらず、殊にジメチロールプロピオン酸から形成されておらず、
(D) 任意に、ブロックされたポリイソシアナートと、トリスアルキルカルバモイルトリアジンと、エポキシ樹脂と、カルボキシ基含有樹脂と、アミノ樹脂(A)とは異なるアミノ基含有樹脂とからなる群から選択される、少なくとも1種の化学的架橋剤、
(E) 任意に、少なくとも1種の有機溶媒、
(F) 任意に、少なくとも1種の触媒、
(G) 任意に、少なくとも1種の塗料に典型的な添加物、
(H) 任意に、少なくとも1種の充填剤、染料及び/又は顔料、
を含み、ここで、成分(B)対(C)の比は、固形分を基準として、1超:1である一成分系アミノ樹脂被覆材料により解決された。
これは、殊に、メラミン−ホルムアルデヒド樹脂、例えば、可塑化されていないメラミン−ホルムアルデヒド樹脂である。可塑化されていないメラミン−ホルムアルデヒド樹脂は、結合剤混合物中の架橋する成分として、単独でも、又は他の化学的に異なる架橋剤、例えばブロックされたポリイソシアナート、トリスアルキルカルバモイルトリアジン(TACT)又はエポキシドと組み合わせても使用される。塗料成分の硬化の後、化学的影響、機械的影響及び天候による影響に対して耐久性の被覆が得られる。可塑化されたメラミン−ホルムアルデヒド樹脂は、カルバマート構造による変性、ポリエステルオール若しくはアルキド樹脂との混合、又はこれらとの初期縮合を伴っていてもよい。可塑化されていないメラミン−ホルムアルデヒド樹脂は、形状安定性でなく柔軟な被覆基材上に使用する場合に、この被覆を引き裂けなくするために、好ましくは外側弾性化を必要とする。唯一の配合物成分としての架橋剤は、一般に、単に脆い網状構造を形成する。
(1) 完全ないし高度にメチロール化され、かつ完全にアルキル化されたないし高度にアルキル化された樹脂(HMMMタイプ)
(2) 部分的にメチロール化され、かつ高度にアルキル化された樹脂(高イミノタイプ)
(3) 部分的にメチロール化され、かつ部分的にアルキル化された樹脂(メチロールタイプ)
(4) 低メチロール化された樹脂(メラミン−ホルムアルデヒド縮合物)
− ヘキサヒドロフタル酸無水物
− トリメチロールプロパン、
− 任意に、少なくとも1種のジオール、
− 任意に、少なくとも1種の他のトリオール、
− 任意に、少なくとも1種の他の二酸若しくは三酸又はこれらの誘導体
の重縮合により得られる。
C1〜C20−アルキル基、例えばメチル、エチル、n−プロピル、イソプロピル、n−ブチル、イソブチル、sec−ブチル、tert−ブチル、n−ペンチル、イソペンチル、sec−ペンチル、ネオペンチル、1,2−ジメチルプロピル、イソアミル、n−ヘキシル、イソヘキシル、sec−ヘキシル、n−ヘプチル、イソヘプチル、n−オクチル、2−エチルヘキシル、トリメチルペンチル、n−ノニル、n−デシル、n−ドデシル、n−オクタデシル、及びn−エイコシル;C3〜C12−シクロアルキル基、例えばシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル、シクロウンデシル及びシクロドデシル;好ましくはシクロペンチル、シクロヘキシル及びシクロヘプチル;アルキレン基、例えばメチレン又はエチリデン;又はC6〜C14−アリール基、例えばフェニル、1−ナフチル、2−ナフチル、1−アントリル、2−アントリル、9−アントリル、1−フェナントリル、2−フェナントリル、3−フェナントリル、4−フェナントリル及び9−フェナントリル、好ましくはフェニル、1−ナフチル及び2−ナフチル、特に好ましくはフェニル。置換されたジカルボン酸の例示的な代表例として、2−メチルマロン酸、2−エチルマロン酸、2−フェニルマロン酸、2−メチルコハク酸、2−オクタデセニルコハク酸、及びこれらの無水物(下記参照)、2−エチルコハク酸、2−フェニルコハク酸、イタコン酸、3,3−ジメチルグルタル酸が挙げられる。更に、上述のジカルボン酸の2種以上の混合物も使用できる。
誘導体とは、好ましくは次のものと解釈される。
− モノマー又はポリマーの形での該当する無水物、
− モノアルキルエステル又はジアルキルエステル、好ましくはモノ−C1〜C4−アルキルエステル又はジ−C1〜C4−アルキルエステル、特に好ましくはモノメチルエステル又はジメチルエステル、又は対応するモノエチルエステル又はジエチルエステル、
− 更にモノビニルエステル及びジビニルエステル、及び
− 混合エステル、好ましくは異なるC1〜C4−アルキル成分との混合エステル、特に好ましくは混合メチルエチルエステル。
C1〜C4−アルキルは、本明細書の範囲内で、メチル、エチル、イソプロピル、n−プロピル、n−ブチル、イソブチル、sec−ブチル、及びtert−ブチル、好ましくはメチル、エチル及びn−ブチル、特に好ましくはメチル及びエチル、更に特に好ましくはメチルを意味する。
− モノマー又はポリマーの形の該当する無水物、
− モノアルキルエステル、ジアルキルエステル若しくはトリアルキルエステル、好ましくはモノ−C1〜C4−アルキルエステル、ジ−C1〜C4−アルキルエステル若しくはトリ−C1〜C4−アルキルエステル、特に好ましくは、モノメチルエステル、ジメチルエステル若しくはトリメチルエステル、又は対応するモノエチルエステル、ジエチルエステル若しくはトリエチルエステル、
− 更に、モノビニルエステル、ジビニルエステル及びトリビニルエステル、
並びに混合エステル、好ましくは異なるC1〜C4−アルキル成分との混合エステル、特に好ましくは混合メチルエチルエステル。
二酸/三酸又はこれらのジアルキルエステルの存在で、これらの構成要素の不在の場合と同じ転化率を得るために、反応時間は明らかに延長されていてよく、かつ/又は反応温度は明らかに高められていてよい。このような構成要素の不在は、製造コストとの関連で好ましいことがある。
(A) アミノ樹脂100質量部(固体割合を基準とする)
(B) ヒドロキシル基含有ポリマー45〜882質量部、好ましくは70〜810質量部(それぞれ固体割合を基準とする)
(C) 分枝したポリエステルポリオール2〜450質量部、好ましくは10〜270質量部(それぞれ固体割合を基準とする)
(D) 任意に、化学的架橋剤、量はタイプ及び系に依存する
(E) 有機溶媒、(A)〜(G)の量の合計を基準として、0〜80質量%、20〜70質量%、特に好ましくは30〜60質量%
(F) 触媒、使用したアミノ樹脂(A)(固体対固体)を基準として、0〜10質量部、好ましくは0.1〜8質量部、特に好ましくは0.3〜6質量部、更に特に好ましくは0.5〜5質量部、殊に1〜3質量部
(G) 任意に、塗料に典型的な添加物、上述のように量はタイプ及び系に依存する
(H) 任意に、充填剤、染料及び/又は顔料、量はタイプ及び系に依存する。
実施例の使用材料:
ヘキサヒドロフタル酸無水物 Aldrich社、融点33℃。使用の前に炉中で溶融
アジピン酸ジメチルエステル Aldrich社、液状
トリメチロールプロパン Aldrich社、白色フレーク、融点56〜58℃
ネオペンチルグリコール 固体、融点127℃
2−ブチル−2−エチル−1,3−プロパンジオール TCI(Tokyo Chemical Industry)社。融点43℃、使用の前に水浴で溶融
Joncryl(登録商標)504:ポリアクリラートオール、OH価140mg KOH/g、キシレン中固体含有率80%;BASF SE、Ludwigshafen
Dynapol(登録商標)LH 832-02 分枝したポリエステルポリオール、ソルベントナフサ150/ブチルグリコール中60%
Luwipal(登録商標)018:殊に自動車用途のための、n−ブタノール中の、n−ブタノールでエーテル化されたメラミン−ホルムアルデヒド樹脂。73%nfA(2g/2h/125℃)。5.5Pa・s(23℃)。BASF SE
Luwipal(登録商標)066 LF:メタノール中の、メタノールでエーテル化されたメラミン−ホルムアルデヒド樹脂(HMMM樹脂)。94.5%nfA(2g/2h/125℃)。4.0Pa・s(23℃)。BASF SE
Nacure(登録商標)2500:アミンで中和されたパラ−トルエンスルホン酸。ブロックされた触媒。King Industries
Nacure(登録商標)2558:ブロックされたパラ−トルエンスルホン酸
Solvenon(登録商標)PM 1−メトキシ−プロパン−2−オール、溶媒、BASF SE
Solvesso(登録商標)150 ExxonMobil Chemical、芳香族溶媒、沸点180〜193℃
GPCを、次の条件で行う:
機器:PSS Agilent Technologies 1260 Infinity
カラム:1×PLGel Mixed E Guard(プレカラム)、長さ5cm、直径0.75cm
1×PLGel Mixed E、長さ30cm、直径0.75cm
1×PLGel Resipore、長さ30cm、直径0.75cm
溶媒:THF
流速:1mL/min
注入体積:50μL
濃度:1g/L
温度:室温(20℃)
実験室試験において、トリメチロールプロパン及びネオペンチルグリコールを反応器内に固体として装入した。ヘキサヒドロフタル酸無水物及び2−ブチル−2−エチル−1,3−プロパンジオールを、溶融した状態で添加した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/ネオペンチルグリコール=1.0:0.5:0.5
還流冷却器及び水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(490.9g)、ネオペンチルグリコール(381.0g)及びヘキサヒドロフタル酸無水物(1128.1g)を窒素雰囲気中で装入し、撹拌しながら160〜180℃に加熱した。5時間の反応時間後でかつ85mg KOH/gの酸価(転化率80%)の達成後に、120℃に冷却し、ブチルアセタート631.3gを添加し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン1.2:1.0
還流冷却器及び水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(840.8g)及びヘキサヒドロフタル酸無水物(1159.2g)を窒素雰囲気中で装入し、撹拌しながら160〜180℃に加熱した。5時間の反応時間後でかつ83mg KOH/gの酸価(転化率81%)の達成後に、120℃に冷却し、ブチルアセタート1017.1gを添加し、更に冷却した。
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(930.7g)及びヘキサヒドロフタル酸無水物(1069.3g)を窒素雰囲気中で室温で装入し、完全に溶融させ、撹拌しながら段階的に160〜180℃に加熱した。約5時間の反応時間後でかつ74mg KOH/gの酸価(転化率82%)の達成後に、120℃に冷却し、ブチルアセタート814gを添加し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/アジピン酸ジメチルエステル=1.0:1.5:0.5 触媒としてオルトチタン酸テトラブチルを用いる
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(778.0g)、ヘキサヒドロフタル酸無水物(596.0g)及びオルトチタン酸テトラブチル(0.5g)を窒素雰囲気中で装入し、撹拌しながら160〜180℃に加熱した。10時間の反応時間後でかつ42mg KOH/gの酸価の達成後に、140℃で、アジピン酸ジメチルエステル(337.0g)を添加した。180℃で更に10時間でかつ22mg KOH/gの酸価の達成後に、120℃に冷却し、ブチルアセタート511.0gを添加し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/2−ブチル−2−エチル−1,3−プロパンジオール=1.2:0.8:0.2
還流冷却器及び水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(330.9g)、溶融した2−ブチル−2−エチル−1,3−プロパンジオール(98.8g)及びヘキサヒドロフタル酸無水物(570.3g)を窒素雰囲気中で装入し、撹拌しながら160〜180℃で加熱した。5時間の反応時間後でかつ98mg KOH/gの酸価(転化率78%)の達成後に、120℃に冷却し、ブチルアセタート407.0gを添加し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン=1.1:1.0
還流冷却器及び水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(530.1g)及びヘキサヒドロフタル酸無水物(669.9g)を窒素雰囲気中で装入し、撹拌しながら160〜180℃に加熱した。5時間の反応時間後でかつ77mg KOH/gの酸価(転化率82%)の達成後に、120℃に冷却し、ブチルアセタート283.3gを添加し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン=1.0:1.0(比較的低い酸価を有する)
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(930.7g)及びヘキサヒドロフタル酸無水物(1069.3g)を窒素雰囲気中で装入し、撹拌しながら160℃に加熱した。この温度を、約30min保持し、その後、180℃に加熱した。約10時間の反応時間後でかつ54mg KOH/gの酸価の達成後に、120℃に冷却し、この生成物をブチルアセタートで75%に希釈し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン=1.0:1.0(比較的低い酸価を有する)
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(465.3g)及びヘキサヒドロフタル酸無水物(534.7g)を窒素雰囲気中で装入し、撹拌しながら160℃に加熱した。この温度を約30min保持し、その後、180℃に加熱した。約8時間の反応時間後でかつ46mg KOH/gの酸価の達成後に、120℃に冷却し、この生成物をブチルアセタート288.4gで70%に希釈し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/2−ブチル−2−エチル−1,3−プロパンジオール=1.0:0.5:0.5
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(22.6g)、2−ブチル−2−エチル−1,3−プロパンジオール(265.90g)及びヘキサヒドロフタル酸無水物(511.5g)を窒素雰囲気中で装入し、撹拌しながら160℃に加熱した。この温度を約30min保持し、その後、180℃に加熱した。約4時間の反応時間後でかつ86mg KOH/gの酸価の達成後に、120℃に冷却し、この生成物をブチルアセタート229.3gで75%に希釈し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/ネオペンチルグリコール=2:1.67:1
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(352.0g)、ネオペンチルグリコール(163.6g)及びヘキサヒドロフタル酸無水物(484.4g)を窒素雰囲気中で装入し、撹拌しながら160℃に加熱した。この温度を約30min保持し、その後、180℃に加熱した。約9時間の反応時間後でかつ41mg KOH/gの酸価の達成後に、160℃に冷却し、3と1/2時間200mbarの真空をかけた。その後、酸価は35mg KOH/gであった。生成物を120℃に冷却し、ブチルアセタート284.64gで70%に希釈し、更に冷却した。
ヘキサヒドロフタル酸無水物/トリメチロールプロパン/ネオペンチルグリコール=2:1:1.27
水分離器を備えた四ツ口フラスコ内に、トリメチロールプロパン(267.6g)、ネオペンチルグリコール(219.9g)及びヘキサヒドロフタル酸無水物(512.5g)を窒素雰囲気中で装入し、撹拌しながら160℃に加熱した。この温度を約30min保持し、その後、180℃に加熱した。約2と1/2時間の反応時間後でかつ62mg KOH/gの酸価の達成後に、160℃に冷却し、1時間200mbarの真空をかけた。その後、酸価は42mg KOH/gであった。この真空を解除し、生成物を120℃に冷却し、ブチルアセタート285.3gで70%に希釈し、更に冷却した。真空下で、冷却器内に若干の昇華物が形成された。
次の特性を試験した:
0%硬化:塗料は、キシレンにより溶解するか又は布によって拭き取ることができる。
50%硬化:塗料は、キシレン及び布により除去されないが、木べらで掻き落とすことができる。
100%硬化:塗料は、木べらによっても除去されない。
勾配炉での測定面は、約10℃に段階分けされている。それぞれ、最初に50%硬化又は100%硬化が測定された温度を記載した。
天然樹脂の製造元 Woerwag社、天然樹脂溶液DBL 5416 No.:701014
パンクレアチン(Merck社、製品番号7130)は、陶製乳鉢中で、VE水と1:1質量%に混合する。
100℃で10〜60分の硬化時間にわたる、ポリオール/Luwipal(登録商標)018=7:3固体/固体の系中での、振り子硬度の進展についてのポリアクリラートオール/本発明によるポリエステルポリオールB1〜B4の混合物と、本発明によるポリエステルポリオールなしのポリアクリラートオールJoncryl(登録商標)504との比較。Luwipal(登録商標)018は、自動車塗料−透明塗料で典型的に使用されているアミノ樹脂である。Joncryl(登録商標)504/ポリエステルポリオールの混合比は、「10:0」(参考);9:1;8:2;7:3固体/固体であった。塗膜は、ガラスプレート上に、フレーム付きブレードを用いて、湿潤で150μmで適用した。フラッシュオフタイムは10分であった。100℃での硬化後の乾燥塗膜の厚みは約40μmであった。振り子硬度測定は、5〜10分後に行った。それぞれ3種の混合物(9:1;8:2;7:3)での4種の全てのポリエステルポリオールにおいて、この振り子硬度は、全体の硬化時間にわたり、ポリエステルポリオールなし(10:0)よりも高い。混合物中に使用されたポリエステルポリオールが多ければそれだけ、振り子硬度はより高くなる。
ポリオール/Luwipal(登録商標)018=7:3固体/固体の系中で、振り子硬度の進展、エリクセン深さ及び架橋密度についてのポリアクリラートオールJoncryl(登録商標)504/本発明によるポリエステルオールB1〜B4の混合物と、本発明によるポリエステルポリオールなしでのポリアクリラートオールJoncryl(登録商標)504との比較。Joncryl(登録商標)504/ポリエステルポリオールの混合比は、9:1;8:2;7:3固体/固体であった。塗膜は、勾配炉用の深絞り用薄板上に、フレーム付きブレードを用いて、湿潤で150μmで適用した。硬化は、10分のフラッシュオフの後に、80〜180℃の温度勾配で20分間、及び(23±2)℃及び(50±10)%の空気湿度で一晩中の貯蔵で行った。乾燥塗膜の厚みは、40〜50μmであった。
耐化学薬品性についてのポリアクリラートオール/本発明によるポリステルポリオールB3の混合物と、ポリエステルポリオールなしのポリアクリラートオールJoncryl(登録商標)504との比較。塗料を、140℃で20分間及び(23±2)℃及び(50±10)%の空気湿度で16〜24時間硬化させた。
ポリエステルポリオールをより多く使用すればそれだけ、耐化学薬品性もより良好になる。耐硫酸性の場合に8:2混合物は参考より悪く、パンクレアチン及び天然樹脂の場合には同じであり、5%苛性ソーダ液の場合には3℃良好であり、つまり平均して同等である。7:3混合物は、硫酸の場合に参考に相応し、その他では耐化学薬品性は参考よりも9〜20℃明らかに良好である。
ポリオール/Luwipal(登録商標)066 LF=4.4:1固体/固体の系中で、コイルコーティング用途についてのポリエステルポリオール/本発明によるポリエステルポリオールB1、B3、B4の混合物と、本発明によるポリエステルポリオールなしのポリエステルポリオールとの比較。Luwipal(登録商標)066 LFは、コイルコーティング塗料で典型的に使用されるアミノ樹脂である。ポリエステルポリオール/本発明によるポリエステルポリオールの混合比は、7:3固体/固体である。塗膜は、スパイラルブレードを用いて、湿潤で50μmで適用した。コイル炉中で300℃で30秒間硬化させ(ピークメタル温度260℃)、及び引き続き(23±2)℃及び(50±10)%の空気湿度で16〜24時間貯蔵した。乾燥塗膜の厚みは20〜22μmであった。
Claims (19)
- 構成成分として
(A) メラミン−ホルムアルデヒド樹脂、ベンゾグアナミン−ホルムアルデヒド樹脂及び尿素−ホルムアルデヒド樹脂からなる群から選択される、少なくとも1種のアミノ樹脂、
(B) ポリ(メタ)アクリラートポリオール(B1)、ポリエステルポリオール(B2)、ポリエーテルオール(B3)、アルキド樹脂(B4)及びポリカルボナートポリオール(B5)からなる群から選択される、少なくとも1種のヒドロキシル基含有ポリマー、
(C)
− ヘキサヒドロフタル酸無水物、
− トリメチロールプロパン、
− 任意に、少なくとも1種のジオール、
− 任意に、少なくとも1種の他のトリオール、
− 任意に、少なくとも1種の他の二酸若しくは三酸又はこれらの誘導体
の重縮合により得られる、少なくとも1種の分枝したポリエステルポリオールであり、かつ、
前記ポリエステルポリオールの原料の酸基及びヒドロキシル基は、1:1〜1:1.95のモル混合比で使用され、かつ
前記ポリエステルポリオール中で、ヘキサヒドロフタル酸無水物を基準として化学量論的に、テトラアルコールは20%未満使用され、かつ
前記ポリエステルポリオールは、ジヒドロキシカルボン酸から形成されておらず、
(D) 任意に、ブロックされたポリイソシアナートと、トリスアルキルカルバモイルトリアジンと、エポキシ樹脂と、カルボキシ基含有樹脂と、アミノ樹脂(A)とは異なるアミノ基含有樹脂とからなる群から選択される、少なくとも1種の化学的架橋剤、
(E) 任意に、少なくとも1種の有機溶媒、
(F) 任意に、少なくとも1種の触媒、
(G) 任意に、少なくとも1種の塗料に典型的な添加物、
(H) 任意に、少なくとも1種の充填剤、染料及び/又は顔料、
からなり、
ここで、成分(B)対(C)の比は、固体を基準として1超:1である、一成分系アミノ樹脂被覆材料。 - 前記アミノ樹脂(A)は、部分的にエーテル化されたメラミン−ホルムアルデヒド樹脂であり、前記部分的にエーテル化されたメラミン−ホルムアルデヒド樹脂は、1:3〜5.4:1.5〜4.3の、メラミン:ホルムアルデヒド:アルコールの組込モル比を有することを特徴とする、請求項1に記載の被覆材料。
- 前記アミノ樹脂(A)は、メラミン:ホルムアルデヒド:アルコールの組込モル比が、1:5.5超:4.5超である、完全にないし高度にメチロール化され、かつ完全にアルキル化されたないし高度にアルキル化されたメラミン−ホルムアルデヒド樹脂であることを特徴とする、請求項1に記載の被覆材料。
- 前記ヒドロキシル基含有ポリマー(B)は、500〜50,000Dの数平均分子量Mnを有するポリ(メタ)アクリラートポリオール(B1)であることを特徴とする、請求項1から3までのいずれか1項に記載の被覆材料。
- 前記ポリマー(B)と前記分枝したポリエステルポリオール(C)とは、固形分を基準にして、1.1:1〜49:1の質量比で使用されることを特徴とする、請求項1から4までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、固形分を基準として、130〜280mg KOH/gのヒドロキシル価を示し、及び/又は前記ポリエステルポリオール(C)は、固形分を基準として、8〜110の、DIN EN ISO 2114:2000による酸価を示し、及び/又は前記ポリエステルポリオール(C)は、200〜400mg KOH/gの、DIN EN ISO 2114:2000による酸価とDIN 53240-2:2007-11によるヒドロキシル価との合計を示すことを特徴とする、請求項1から5までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、1:1.1〜1:1.6の酸基対ヒドロキシル基のモル混合比で、専ら、ヘキサヒドロフタル酸無水物とトリメチロールプロパンとから製造されることを特徴とする、請求項1から6までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、ヘキサヒドロフタル酸無水物の他に、別の二酸若しくは三酸又はこれらの誘導体を使用しないで製造されることを特徴とする、請求項1から7までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、専ら、ヘキサヒドロフタル酸無水物と、トリメチロールプロパンと、トリシクロデカンジメタノール、テトラヒドロ−2,5−ビス−(ヒドロキシメチル)−フラン、1,6−ヘキサンジオール、ネオペンチルグリコール及び2−ブチル−2−エチル−1,3−プロパンジオールの異性体又は異性体混合物からなる群から選択されるジオールとから形成されていることを特徴とする、請求項1から8までのいずれか1項に記載の被覆材料。
- 前記トリメチロールプロパンのヒドロキシル基対前記ジオールのヒドロキシル基のモル比は、1超:1であることを特徴とする、請求項9に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、スズ不含であり、及び/又は触媒作用なしで又は亜鉛、チタン、ジルコニウム若しくはビスマスを含む触媒を用いて、又はスズを含まない他の触媒を用いて製造されている、及び/又は前記ポリエステルポリオール(C)は、溶媒の不在で製造されることを特徴とする、請求項1から10までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、500〜4000g/molの数平均分子量Mn、及び/又は5以下の多分散度を有することを特徴とする、請求項1から11までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、−20〜50℃のガラス転移温度を示すことを特徴とする、請求項1から12までのいずれか1項に記載の被覆材料。
- 前記ポリエステルポリオール(C)は、一段階プロセスで製造されることを特徴とする、請求項1から13までのいずれか1項に記載の被覆材料。
- 前記構成成分を、次の量で含む:
(A) 前記アミノ樹脂100質量部(固体割合を基準とする)
(B) 前記ヒドロキシル基含有ポリマー45〜882質量部(それぞれ固体割合を基準とする)
(C) 前記分枝したポリエステルポリオール2〜450質量部(それぞれ固体割合を基準とする)
(D) 任意に、化学的架橋剤
(E) 有機溶媒、(A)〜(G)の量の合計を基準として0〜80質量%、
(F) 触媒、使用したアミノ樹脂(A)(固体対固体)を基準として0〜10質量部、
(G) 任意に、塗料に典型的な添加物、
(H) 任意に、充填剤、染料及び/又は顔料
ことを特徴とする、請求項1から14までのいずれか1項に記載の被覆材料。 - 請求項1から15までのいずれか1項に定義されたアミノ樹脂(A)及びポリマー(B)及びポリエステルポリオール(C)を1:1〜1:9の、(A):(B)と(C)との合計の質量比で互いに混合し、ここで、任意に、更に他の成分(D)〜(H)を混入することができ、かつ引き続き基材に施すことを特徴とする、基材の被覆方法。
- 建築部材、車両又は飛行機の被覆のため、缶コーティング用、コイルコーティング用又は装飾塗装用の、請求項1から15までのいずれか1項に記載の被覆材料の使用。
- 木材、ベニア、紙、ボール紙、厚紙、繊維素材、シート、皮革、不織布、プラスチック表面、ガラス、セラミック、金属及び鉱物質の建築材料、例えばセメントレンガ又は繊維セメントボードから選択される基材の被覆のための、ここで、前記基材は、それぞれ、任意に、予備被覆又は前処理されていてよい、請求項1から15までのいずれか1項に記載の被覆材料の使用。
- 一成分系アミノ樹脂被覆材料で被覆された、基材であって、
前記被覆材料が、構成成分として
(A) メラミン−ホルムアルデヒド樹脂、ベンゾグアナミン−ホルムアルデヒド樹脂及び尿素−ホルムアルデヒド樹脂からなる群から選択される、少なくとも1種のアミノ樹脂、
(B) ポリ(メタ)アクリラートポリオール(B1)、ポリエステルポリオール(B2)、ポリエーテルオール(B3)、アルキド樹脂(B4)及びポリカルボナートポリオール(B5)からなる群から選択される、少なくとも1種のヒドロキシル基含有ポリマー、
(C)
− ヘキサヒドロフタル酸無水物、
− トリメチロールプロパン、
− 任意に、少なくとも1種のジオール、
− 任意に、少なくとも1種の他のトリオール、
− 任意に、少なくとも1種の他の二酸若しくは三酸又はこれらの誘導体
の重縮合により得られる、少なくとも1種の分枝したポリエステルポリオールであり、かつ、
前記ポリエステルポリオールの原料の酸基及びヒドロキシル基は、1:1〜1:1.95のモル混合比で使用され、かつ
前記ポリエステルポリオール中で、ヘキサヒドロフタル酸無水物を基準として化学量論的に、テトラアルコールは20%未満使用され、かつ
前記ポリエステルポリオールは、ジヒドロキシカルボン酸から形成されておらず、
(D) 任意に、ブロックされたポリイソシアナートと、トリスアルキルカルバモイルトリアジンと、エポキシ樹脂と、カルボキシ基含有樹脂と、アミノ樹脂(A)とは異なるアミノ基含有樹脂とからなる群から選択される、少なくとも1種の化学的架橋剤、
(E) 任意に、少なくとも1種の有機溶媒、
(F) 任意に、少なくとも1種の触媒、
(G) 任意に、少なくとも1種の塗料に典型的な添加物、
(H) 任意に、少なくとも1種の充填剤、染料及び/又は顔料、
からなり、
ここで、前記ポリエステルポリオール(C)は、200〜400mg KOH/gの、DIN EN ISO 2114:2000による酸価とDIN 53240-2:2007-11によるヒドロキシル価との合計を示す、前記基材。
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JP2004026940A (ja) * | 2002-06-24 | 2004-01-29 | Toyota Motor Corp | 水性白色ソリッドカラー塗料 |
JP5118326B2 (ja) * | 2006-10-13 | 2013-01-16 | 日本ペイント株式会社 | 積層塗膜の形成方法 |
DE102007026722A1 (de) | 2007-06-06 | 2008-12-11 | Basf Coatings Japan Ltd., Yokohama | Klarlackzusammensetzungen enthaltend hyperverzweigte, dendritische hydroxyfunktionelle Polyester |
JP5498002B2 (ja) | 2007-09-19 | 2014-05-21 | 関西ペイント株式会社 | 自動車用水系塗料 |
CA2741414C (en) * | 2008-10-21 | 2013-12-31 | Kansai Paint Co., Ltd. | Method for forming a multilayer paint film |
US9029460B2 (en) * | 2009-02-06 | 2015-05-12 | Stacey James Marsh | Coating compositions containing acrylic and aliphatic polyester blends |
US8568833B2 (en) * | 2009-09-29 | 2013-10-29 | Kansai Paint Co., Ltd. | Process for formation of multi-layered coating film |
CN103497656B (zh) * | 2013-10-14 | 2014-12-24 | 湖南湘江关西涂料有限公司 | 一种汽车本色面漆及其制备方法 |
-
2014
- 2014-09-29 EP EP20140186902 patent/EP2837667A3/de not_active Withdrawn
-
2015
- 2015-08-06 ES ES15750334T patent/ES2946111T3/es active Active
- 2015-08-06 JP JP2017517020A patent/JP6651509B2/ja active Active
- 2015-08-06 CN CN201580064225.6A patent/CN107001849B/zh active Active
- 2015-08-06 WO PCT/EP2015/068125 patent/WO2016050396A1/de active Application Filing
- 2015-08-06 BR BR112017006267A patent/BR112017006267A2/pt not_active Application Discontinuation
- 2015-08-06 KR KR1020177011549A patent/KR102468281B1/ko active IP Right Grant
- 2015-08-06 US US15/515,051 patent/US10472539B2/en active Active
- 2015-08-06 RU RU2017115225A patent/RU2017115225A/ru not_active Application Discontinuation
- 2015-08-06 EP EP15750334.3A patent/EP3201280B1/de active Active
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Also Published As
Publication number | Publication date |
---|---|
EP2837667A3 (de) | 2015-04-22 |
US20190016915A1 (en) | 2019-01-17 |
KR20170066493A (ko) | 2017-06-14 |
EP2837667A2 (de) | 2015-02-18 |
KR102468281B1 (ko) | 2022-11-18 |
ZA201702815B (en) | 2018-08-29 |
BR112017006267A2 (pt) | 2017-12-12 |
EP3201280B1 (de) | 2023-05-24 |
RU2017115225A (ru) | 2018-11-06 |
ES2946111T3 (es) | 2023-07-12 |
CN107001849A (zh) | 2017-08-01 |
US10472539B2 (en) | 2019-11-12 |
EP3201280A1 (de) | 2017-08-09 |
WO2016050396A1 (de) | 2016-04-07 |
CN107001849B (zh) | 2020-03-06 |
RU2017115225A3 (ja) | 2019-03-07 |
JP2017535631A (ja) | 2017-11-30 |
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